Our invention relates to controlled time-release microparticulate active and bioactive compositions (including perfuming compositions) for targeted delivery to services such as skin, hair and fabric and the environment proximate thereto. The active and bioactive materials contained in the microparticulate compositions of our invention have a calculated log.sub.10 P of between 1 and 8 (P being the n-octanol-water partition coefficient of the active and bioactive materials). Such compositions include the active or bioactive material in single phase solid solution in a wax or polymer matrix also having coated thereon and/or containing a compatible surfactant. Certain combinations of surfactants useful in the practice of our invention are novel, for the surfactants include partially hydrolyzed polyvinyl acetate. Other materials, to wit: tetra(2-hydroxypropyl) ethylenediamine having the structure: ##STR1## is not only useful as a surfactant, but also increases the substantivity of fragrances.
Many household products, personal products and health care products contain active and bioactive products which need to be delivered to and deposited on a target surface, i.e., fabric, skin, hair and other living tissues. Once deposited on the target surface, there is a need for the active product, i.e., a fragrance, flavor or drug, to controllably and sustainably released over a long period of time in an efficacious manner.
Publications in the prior art indicate attempts to fulfill the foregoing needs. However, no engineered coordination of the utilization of the variables concerned has been shown in the prior art whereby, depending on the changing (as a function of time) physical and chemical properties of the surface treated and surrounding environment, the chemical and physical nature of the active and bioactive product (including diffusivities taken alone and in combination with one another in various delivery systems), the controlled time release particle composition, the controlled time release particle size range and the required rate of controlled time release of the active and bioactive product to the surface and environment surrounding the active or bioactive product delivery composition, the delivery system is shown to be capable of being optimally designed and easily and commercially manufactured.
Young, U.S. Pat. No. 4,152,272 issued on May 1, 1979 discloses fabric conditioning compositions containing particles of size 0.1 to 200 microns and of melting point 38.degree. C. to 150.degree. C. and comprising a wax-like carrier substance and a perfume. The particles are distributed throughout a composition, especially an aqueous fabric softening composition which contains a fabric-substantive cationic surfactant. An example of the cationic surfactant of Young is cetyl trimethyl ammonium bromide cited at column 6, lines 23 and 24. Young, however, shows formation of wax/perfume particles using, for example, a colloid mill as is shown at column 8, lines 60-65.
Domb, U.S. Pat. No. 5,188,837 issued on Feb. 23, 1993 discloses a microsuspension system and method for its preparation. The microsuspension contains lipospheres which are solid, water-insoluble microparticles that have a layer of a phospholipid embedded on their surface. The core of the liposphere is a solid substance to be delivered or a substance to be delivered that is dispersed in an inert solid vehicle such as a wax.
Trinh, et al, U.S. Pat. No. 5,540,853 issued on Jul. 30, 1996 discloses a personal cleansing composition comprising:
(a) from about 0.001% up to about 10% by weight of an enduring perfume composition having at least about 70% components with a calculated log.sub.10 P.gtoreq.3 and a boiling point of .gtoreq.250.degree. C.; PA1 (b) from about 0.01% up to about 95% by weight of a surfactant system; and PA1 (c) the balance comprising carrier PA1 I. a solid particulate composition comprising: PA1 II. a liquid composition comprising: PA1 and wherein the dispersibility modifier affects the viscosity, dispersibility or both. PA1 (i) a single phase solid solution of a matrix material which is in the alternative at least one of a hydrophobic polymer and/or at least one hydrophobic wax, each of which polymer and wax has a melting point in the range of from about 35.degree. C. up to about 120.degree. C. at 1 atmosphere pressure, having dissolved therein at least one active or bioactive substance (for example, a fragrance material) which is hydrophobic, said solid solution having an outer surface and an internal matrix volume; and PA1 (ii) proximate to substantially to the entirety of said outer surface a substantially hydrophilic surfactant. PA1 (a) the substantially hydrophilic surfactant may be substantially entirely coated on and fixedly bonded to the entirety of the outer surface of the single phase solid solution in the form of a continuous submicron layer of surfactant; or PA1 (b) the substantially hydrophilic surfactant may be located proximate to and immediately, substantially beneath the entirety of the outer surface of the solid solution and substantially within the said internal matrix volume; and PA1 (c) the substantially hydrophilic surfactant is both (a) substantially, entirely coated on and fixedly bonded to the entirety of the outer surface of the single phase solid solution in the form of a continuous submicron layer of surfactant and (b) located proximate to and immediately, substantially beneath the entirety of the outer surface of the solid solution and substantially within the internal matrix volume. PA1 (a) the cationic modified starch, RediBOND.RTM. 5320 (trademark of the National Starch Company of Bridgewater, N.J.), in admixture with partially hydrolyzed polyvinyl acetate having a degree of hydrolysis of between about 73% up to about 99% and having a molecular weight in the range of from about 5,000 up to about 67,000; PA1 (b) the substance tetra (2-hydroxypropyl) ethylenediamine (marketed, for example, as QUADROL.RTM. Polyol, and having the structure: ##STR3## (c) cetyl trimethyl ammonium halide, including cetyl trimethyl ammonium chloride having the structure: ##STR4## (d) a quaternary ammonium polysilane derivative having the structure: ##STR5## wherein R is the moiety having the structure: ##STR6## wherein x is an integer of from 10 up to 100 and m is an integer of from 10 up to 100 in admixture with partially hydrolyzed polyvinyl acetate being hydrolyzed to the extent of from about 73% up to about 99% and having a molecular weight in the range of from about 5,000 up to about 67,000; and PA1 (e) the cationic polysaccharide derivative defined according to the structure: ##STR7## wherein n is an integer of from 1 up to 3; R.sup.11 and R.sup.12 are independently an alkyl, aryl, aralkyl or alkaryl group when n is 1; R.sup.11 or R.sup.12 is one of the groups when n is 2; or R.sup.11 and R.sup.12 are not present when n is 3; and wherein the moiety "SACCH" represents a starch or cellulose moiety. PA1 (a) polyamides having a molecular weight in the range of from about 6,000 up to about 12,000, for example, MACROMELT.RTM. 6030 manufactured by the Henkel Ag. of Dusseldorf, Germany (other examples being set forth in Lindauer, et al, U.S. Pat. No. 4,184,099 issued on Jan. 15, 1980, the specification for which is incorporated by reference herein and including the VERSALON.RTM. line of polyamide polymers manufactured by the Henkel Corporation of Minneapolis, Minn.); PA1 (b) synthetic and natural carnauba wax; PA1 (c) synthetic and natural candelilla wax; PA1 (d) mixtures of cetyl palmitate (marketed, for example, as CUTINA.RTM. wax) with carnauba wax; PA1 (e) mixtures of cetyl palmitate and candelilla wax; PA1 (f) ozokerite wax; PA1 (g) ceresin wax; and PA1 (h) low density polyethylene wax having a molecular weight in the range of from about 500 up to about 6,000. PA1 (a) with respect to the bottom note components, the vapor pressure range should be from 0.0001 mm/Hg up to 0.009 mm/Hg at 25.degree. C.; PA1 (b) with respect to the middle note components, the vapor pressure range of the middle note components should be from 0.01 mm/Hg up to 0.09 mm/Hg at 25.degree. C.; and PA1 (c) with respect to the topnote components, the vapor pressure range of the topnote components should be from 0.1 mm/Hg up to 2.0 mm/Hg at 25.degree. C. PA1 (a) GALAXOLIDE.RTM., a mixture of compounds having the structures: ##STR9## (b) geraniol having the structure: ##STR10## (c) .beta.-pinene having the structure: ##STR11## (d) n-octanal having the structure: ##STR12## (e) dihydromyrcenol having the structure: ##STR13## (f) KOAVONE.RTM. (trademark of International Flavors & Fragrances Inc. of New York, N.Y.) having the structure: ##STR14## (g) eugenol having the structure: ##STR15## PA1 (i) intimately admixing at least one hydrophobic active ingredient or bioactive ingredient material with at least one hydrophobic polymer and/or at least one hydrophobic wax to form a first mixture at a temperature greater than or equal to the melting point of said polymer or said wax or, in the case of mixtures, the melting point of the highest melting polymer or wax in the mixture; PA1 (ii) intimately admixing a surfactant (as defined, supra) with an aqueous composition comprising water (for example, a mixture of sodium chloride and water or a mixture of propylene glycol and water or water itself) to form a second mixture which is an aqueous solution (for example, a solution of sodium chloride in water or a solution of propylene glycol in water); PA1 (iii) blending said first mixture and said second mixture at a temperature in the range of from about 60.degree. C. up to the boiling point at atmospheric pressure of the aqueous composition (for example, water boiling at 100.degree. C. or a mixture of water and propylene glycol boiling at 120.degree. C.) whereby a microemulsion is formed; and PA1 (iv) causing the hydrophobic active ingredient- or bioactive ingredient (e.g., perfume)-containing composition in the solid phase to form as an aqueous suspension of solid phase particles (as by cooling to 25.degree. C.) PA1 (i) intimately admixing at least one hydrophobic active or bioactive material (e.g., perfume composition) with (a) at least one hydrophobic polymer and/or at least one hydrophobic wax and (b) at least one surfactant to form a first single liquid phase mixture at a temperature greater than or equal to the melting point of said polymer or said wax or, in the case of mixtures, the melting point of the highest melting polymer or wax in the mixture; PA1 (ii) blending said first single liquid phase mixture with an aqueous composition comprising water (for example, water itself or a mixture of propylene glycol and water or a mixture of sodium chloride and water, for example, a 5% sodium chloride solution or a 20% aqueous propylene glycol solution) whereby a microemulsion is formed; and PA1 (iii) causing the hydrophobic active or bioactive ingredient-containing composition (e.g., a perfume-containing composition or an aroma chemical-containing composition) in the solid phase to form as an aqueous suspension of solid phase particles (for example, cooling the resulting suspension to a temperature in the range of from about 10.degree. C. up to about 30.degree. C.) PA1 (i) means for intimately admixing at least one hydrophobic active ingredient- or bioactive ingredient-containing material with at least one hydrophobic polymer or at least one hydrophobic wax to form a first single liquid phase mixture at a temperature greater than or equal to the melting point of said polymer or said wax or, in the case of mixtures, the highest melting component of the mixture; PA1 (ii) means for intimately admixing a surfactant with an aqueous composition comprising water to form a second mixture which is an aqueous solution (for example, using a homogenizer or rotor/stator high shear mixer); PA1 (iii) means for blending said first mixture and said second mixture at a temperature of between 60.degree. C. and the boiling point of the aqueous composition at atmospheric pressure whereby a microemulsion is formed (for example, using the homogenizer and/or the rotor/stator high shear mixer as described, supra); and PA1 (iv) means for causing the hydrophobic active ingredient- or bioactive ingredient-containing composition in the solid phase to form as an aqueous suspension of solid phase particles (for example, using cooling means to cool the mixture to 10-30.degree. C., for example, using apparatus equipped with cooling coils). PA1 (i) means for intimately admixing at least one hydrophobic active ingredient- or bioactive ingredient-containing composition with (a) at least one hydrophobic polymer and/or at least one hydrophobic wax and (b) at least one surfactant to form a first single liquid phase mixture at a temperature greater than or equal to the melting point of said polymer or said wax or, in the case of mixtures, the melting point of the highest melting of the materials in the mixture; PA1 (ii) means for blending said first single liquid phase mixture with an aqueous composition comprising water whereby a microemulsion is formed (for example, using the homogenizer and/or the rotor/stator high shear mixer as described, supra); and PA1 (iii) means for causing the hydrophobic active ingredient- or bioactive ingredient-containing composition in the solid phase to form as an aqueous suspension of solid phase particles (for example, cooling coils to cool the suspension to a temperature of between 10.degree. C. and 30.degree. C.).
wherein the pH is from about 4 up to about 11. Trinh, et al, however, does not disclose a particulate control time release delivery system containing active, bioactive or perfuming materials which have a calculated log.sub.10 P in the range of from 1 up to about 8. The disclosure of Trinh, et al, U.S. Pat. No. 5,540,853 is incorporated by reference herein.
Somasundaran, et al, U.S. Pat. No. 5,476,660 issued on Dec. 19, 1995 discloses compositions to deposit an active substance on a target surface. The active substance is left on the surface after the product is rinsed off the surface. The preferred deposition is from compositions containing an anionic or nonionic active in the co-presence of an anionic surfactant. The compositions contain carrier particles having a zwitterionic or cationic surface and a plurality of outwardly protruding filaments containing charged organocarbyl groups. The active substance is contained within the carrier particles. Examples of target surfaces are mammalian skin, hair or nails.
Bacon, et al, U.S. Pat No. 5,652,206 issued on Jul. 29, 1997 discloses a rinse-added fabric softening composition selected from the group consisting of:
(A) from about 50% to about 95% of biodegradable cationic quaternary ammonium fabric softening compound: PA2 (B) from about 0.01% to about 15% of an enduring perfume comprising at least 70% of enduring perfume ingredients selected from the group consisting of: ingredients having a boiling point of at least about 250.degree. C. and a ClogP of at least about 3, wherein ClogP is the calculated octanol/water partitioning coefficient as the logarithm to the base 10.logP, said ingredients having a boiling point of at least 250.degree. C. and a ClogP of at least about 3 being less than 70% by weight of said enduring perfume so that a perfume with only ingredients having a boiling point of at least about 250.degree. C. and a ClogP of at least about 3 will not be an enduring perfume; cis-jasmone; dimethyl benzyl carbinyl acetate; ethyl vanillin; geranyl acetate; .alpha.-ionone; .beta.-ionone; .gamma.-ionone; KOAVONE.RTM.; lauric aldehyde; methyl dihydrojasmonate; methyl nonyl acetaldehyde; .gamma.-nonalactone; phenoxy ethyl iso-butyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethyl carbinyl acetate; .alpha.-methyl-4-(2-methylpropyl)benzenepropanal; 6-acetyl-1,1,3,4,4,6-hexamethyl tetrahydronaphthalene; undecylenic aldehyde; vanillin; 2,5,5-trimethyl-2-pentyl-cyclopentanone; 2-tert-butylcyclohexanol; verdox; para-tert-butylcyclohexyl acetate; and mixtures thereof; PA2 (C) optionally, from about 0% to about 30% of dispersibility modifier; and PA2 (D) optionally, from about 0% to about 15% of a pH modifier; and PA2 (A) from about 0.5% to about 80% of biodegradable cationic fabric softening compound; PA2 (B) from about 0.01% to about 10% of an enduring perfume comprising at least 70% of enduring perfume ingredients selected from the group consisting of: ingredients having a boiling point of at least about 250.degree. C. and a ClogP of at least 3, said ingredients having a boiling point of at least about 250.degree. C. and a ClogP of at least about 3 being less than 70% by weight of said enduring perfume so that a perfume with only ingredients having a boiling point of at least about 250.degree. C. and a ClogP of at least about 3 will not be an enduring perfume; cis-jasmone; dimethyl benzyl carbinyl acetate; ethyl vanillin; geranyl acetate; .alpha.-ionone; .beta.-ionone; .gamma.-ionone; KOAVONE.RTM.; lauric aldehyde; methyl dihydrojasmonate; methyl nonyl acetaldehyde; .gamma.-nonalactone; phenoxy ethyl isobutyrate; phenyl ethyl dimethyl carbinol; phenyl ethyl dimethyl carbinyl acetate; .alpha.-methyl-4-(2-methylpropyl)-benzenepropanal; 6-acetyl-1,1,3,4,4,6-hexamethyl tetrahydronaphthalene; undecylenic aldehyde; vanillin; 2,5,5-trimethyl-2-pentylcyclopentanone; 2-tert-butylcyclohexanol; verdox; para-tert-butylcyclohexyl acetate; and mixtures thereof; PA2 (C) optionally, from about 0% to about 30% of dispersibility modifier; and PA2 (D) the balance comprising a liquid carrier selected from the group consisting of water, C.sub.1-4 monohydric alcohol; C.sub.2-6 polyhydric alcohol; propylene carbonate; liquid polyethylene glycols; and mixtures thereof;
The Bacon, et al reference does not disclose or infer the control time release system of our invention wherein the particles, each consisting of a solid solution of a hydrophobic polymer and/or a hydrophobic wax contain and deliver active, bioactive or fragrance materials to a solid surface and to the environment surrounding same which active, bioactive and perfuming materials have a calculated log.sub.10 P in the range of from 1 up to about 8.
Kamel, et al, U.S. Pat. No. 4,919,841 issued on Apr. 24, 1990 discloses a process for preparing encapsulated active particles by the steps of: dispersing active materials in molten wax; emulsifying the active/wax dispersion in an aqueous surfactant solution for no longer than 4 minutes; quenching the capsules by cooling; and retrieving solidified capsules. Examples of active materials are fragrances. Kamel, et al, however, does not show the specific formation of single phase solid solutions of matrix materials containing at least one hydrophobic polymer and/or at least one hydrophobic wax having dissolved therein at least one hydrophobic fragrance material controllably time releasable therefrom and having a calculated log.sub.10 P in the range of from about 1 up to about 8.
Henkel (Wahle, et al), PCT Published Application No. 95/11936 published on Oct. 20, 1994 discloses finely dispersed wax dispersions with a long shelf life which can be obtained by heating: (A) 10 to 80 weight percent of a wax with (B) 0.5 to 30 weight percent of a hydrophilic nonionic dispersant with an HLB value of 8 to 18 and (C) 1 to 30 weight percent of a hydrophobic co-dispersant from the group of fatty alcohols with 12-22 carbon atoms or the partial esters of polyols with 3-6 carbon atoms with fatty acids with 12-22 carbon atoms, and then heating the dispersion obtained to a temperature within or above the phase inversion point or producing a dispersion directly at this temperature and subsequently cooling the dispersion to a temperature below the phase inversion range. PCT Application No. 95/11936 does not, however, disclose the particulate composition of our invention containing a single phase solid solution of a hydrophobic polymer and/or a hydrophobic wax having dissolved therein at least one hydrophobic fragrance material, capable of delivering the fragrance material to a surface and to the environment surrounding the particulate composition and wherein the fragrance has a log.sub.10 P of between about 1 and about 8.
Donbrow, Microcapsules and Nanoparticles in Medicine and Pharmacy, Chapter 6, "NANOPARTICLES--PREPARATION AND APPLICATIONS", Jorg Kreuter (pages 126-148), CRC Press, 1992, discloses the production of nanoparticles containing bioactive materials by means of emulsion polmerization. The Donbrow reference does not explicitly or implicitly disclose the novel process for preparing the novel compositions of matter of our invention.
Adeyeye et al, "Development and Evaluation of Sustained-Release Ibuprofen Wax Microspheres. I. Effect of Formulation Variables on Physical Characteristics", Pharm. Res. (1991), Volume 8, No. 11, pages 1377-1383, discloses the use of a congealable disperse phase encapsulation method for preparing sustained-release ibuprofen-wax microspheres. The microspheres are prepared with paraffin wax such as ceresine and mycrocrystalline waxes using polyvinylpyrrolidone as a dispersant and using stearyl alcohol as a wax modifier. Adeyeye, et al does not infer or disclose the microparticulate compositions of matter of our invention containing active or bioactive materials having a calculated log.sub.10 P in the range of from 1 up to about 8.
Thus, nothing in the prior art discloses compositions for effecting the targeted delivery of bioactive or active substances to substantially solid surfaces wherein a substance comprises at least one substantially ellipsoidal hydrophobic particle consisting essentially of a single phase solid solution of a hydrophobic polymer or a hydrophobic wax having dissolved therein at least one active or bioactive material and having proximate to substantially the entirety of its outer surface a substantially hydrophilic surfactant wherein the calculated log.sub.10 P of the active or bioactive substance is in the range of from about 1 up to about 8.